JP6988673B2 - Copper alloy target and its manufacturing method - Google Patents

Description

The present invention mainly relates to a copper alloy target used for forming an electrode film, a wiring film, etc. of an electronic component, and a method for manufacturing the same.

Generally, electrode films, wiring films, and the like are formed on various electronic components.

The electrode film and wiring film are often formed by printing with a conductive paste or plating. However, as the size of electronic components becomes smaller and the electrode film and wiring film to be formed become thinner and thinner, targets such as copper alloys that can form the electrode film and wiring film thinner than the plating film are targeted. The forming method by sputtering used is used.

Regarding the copper alloy target for forming a wiring film by sputtering, for example, in the following Patent Document 1, for a wiring film of a touch panel sensor containing 0.1 to 40 atomic% of nickel and the balance being composed of copper and unavoidable impurities. Copper alloy targets are disclosed.

Japanese Unexamined Patent Publication No. 2013-120411

In general, a copper alloy target is made by vacuuming a sealable chamber such as a high-frequency vacuum melting furnace, and then introducing an inert gas such as argon gas or nitrogen gas to make copper or other metal into a predetermined component. The material is melted to prepare a molten copper alloy, and the prepared molten copper alloy is used for casting to obtain a columnar (generally, columnar) copper alloy ingot.
When industrially mass-producing copper alloy targets, columnar copper alloy ingots obtained by forging are forged, rolled, and cut to form a plate, and then machined to a predetermined length. Complete as a product with width and thickness.

However, when sputtering is performed using a copper alloy target made of copper and nickel manufactured by the above manufacturing method, the copper constituting the electrode film, wiring film, etc. formed by sputtering depends on the difference in the elapsed time used for sputtering. The composition of the alloy and the characteristics of the electrode film and the wiring film (for example, the electric resistance value, etc.) may vary.
In recent years, the miniaturization of electronic parts has progressed, and the size and shape of electrode films and wiring films have also become finer. The required characteristic range of the miniaturized electrode films and wiring films is extremely high. It is getting narrower.

The present invention has been made in view of such a problem, and the variation in the composition of the copper alloy constituting the electrode film, the wiring film, etc. formed by the sputtering due to the difference in the elapsed time used for the sputtering is suppressed as much as possible. It is an object of the present invention to provide a copper alloy target capable of minimizing the variation in characteristics of an electrode film, a wiring film, and the like, and a method for manufacturing the same.

The present inventors have made further diligent studies in order to solve the above-mentioned problems. As a result, in the manufacturing process of the copper alloy target, the copper alloy ingot obtained by the casting process is subjected to a predetermined treatment, so that the electrode film formed by the sputtering is formed even if the elapsed time used for the sputtering is different. We have found that the variation in the composition of the copper alloy constituting the wiring film and the like can be suppressed as much as possible, and the variation in the characteristics of the electrode film, the wiring film and the like can be minimized, and the present invention has been completed. That is, the present invention provides the following.

(1) The first invention of the present invention is a copper alloy target comprising an alloy of copper and nickel and containing nickel in a proportion of more than 10% by mass and 50% by mass or less, wherein the copper alloy is contained. The difference between the nickel content at each position in the entire region of the target and the average value of the nickel content in the entire region of the copper alloy target is the average value of the nickel content in the entire region of the copper alloy target. It is a copper alloy target characterized in that the absolute value of the percentage divided by 3% or less.

(2) In the second invention of the present invention, in the first invention, the nickel content at each position in the entire region of the copper alloy target and the nickel content in the entire region of the copper alloy target. The absolute value of the percentage obtained by dividing the difference from the average value of the copper alloy target by the average value of the nickel content in the entire region of the copper alloy target is 1% or less.

(3) The third invention of the present invention is a step of melting copper and nickel in a vacuum melting furnace to prepare a molten copper alloy, and casting using the prepared molten copper alloy to cast a columnar copper alloy. A similar region having a similarity ratio of 5% to 10% with respect to the bottom surface from the center of the bottom surface of the copper alloy ingot to the outer edge of the bottom surface after the step of producing the ingot and the copper alloy ingot. The step of removing the central columnar portion from the copper alloy ingot, which has at least the same height as the copper alloy ingot, and the height of the copper alloy ingot after producing the copper alloy ingot. It is a method for manufacturing a copper alloy target, which comprises a step of cutting in half along a direction.

(4) In the fourth invention of the present invention, in the third invention, the copper alloy ingot from which the central columnar portion is removed and cut in half along the height direction is subjected to 1,000 ° C. or higher. It is a method for manufacturing a copper alloy target, which comprises a step of heating to a first temperature lower than the melting point of copper and forging the copper alloy ingot heated to the first temperature.

(5) In the fifth aspect of the present invention, in the fourth aspect, the forged copper alloy ingot is heated to a second temperature within the range of 900 ° C. ± 100 ° C. and heated to the second temperature. This is a method for manufacturing a copper alloy target, which comprises a step of repeatedly performing hot rolling by changing the processing ratio of the copper alloy ingot in multiple stages to form a plate body having a first thickness.

(6) In the sixth invention of the present invention, in the fifth invention, the hot-rolled plate body is cold-rolled so as to have a processing ratio of 5% or more, and the plate body has a second thickness. This is a method for manufacturing a copper alloy target, which comprises a step of heat-treating the plate body and then machining the heat-treated plate body to complete a product of the copper alloy target.

According to the present invention, the variation in the composition of the copper alloy constituting the electrode film, the wiring film, etc. formed by sputtering due to the difference in the elapsed time used for sputtering is suppressed as much as possible, and the characteristics of the electrode film, the wiring film, etc. are exhibited. A copper alloy target capable of minimizing variation and a method for producing the same can be obtained.

It is explanatory drawing which shows roughly the position where the copper alloy ingot is cut, and the part which is removed from the copper alloy ingot in the manufacturing method of the copper alloy target of this invention. In the explanatory view which shows the measurement position of the nickel content in the plate body used as the copper alloy target which concerns on each Example of this invention, (a) is specified in the length direction and the width direction of the plate body of Example 1. (B) is a plan view showing each measurement position to be measured, (b) is a plan view showing each measurement position specified in the length direction and the width direction of the plate body of Example 2, (c) is (a), (b). It is sectional drawing which shows each measurement position specified in the width direction and the thickness direction of each plate body. In the explanatory view which shows the measurement position of the nickel content in the plate body used as the copper alloy target which concerns on each comparative example of this invention, (a) is specified in the length direction and width direction of the plate body of comparative example 1. (B) is a plan view showing each measurement position to be measured, (b) is a plan view showing each measurement position specified in the length direction and the width direction of the plate body of Comparative Example 2, (c) is (a), (b). It is sectional drawing which shows each measurement position specified in the width direction and the thickness direction of each plate body. It is explanatory drawing which shows an example of the electric resistance value measuring method with respect to the coating film formed on the glass substrate by sputtering film formation using the copper alloy target of each Example and comparative example of this invention. It is an explanatory diagram showing the measurement position of the nickel content in the copper alloy ingot used in the production of the conventional copper alloy target, (a) is a diagram showing the position where the copper alloy ingot is cut, and (b) is (a). ) Is a cross-sectional view showing the measurement position of the nickel content at each position specified in the length direction and the height direction of the bottom surface in the cross section of the copper alloy ingot cut at the position shown in).

Prior to the description of the embodiment, the process leading to the derivation of the copper alloy target of the present invention and the method for producing the same will be described.

As described above, conventionally, when a copper alloy target is industrially mass-produced, a metal material (copper and nickel in the present invention) is melted to prepare a molten copper alloy, and the prepared molten copper alloy is used for casting. , Columnar (generally columnar) copper alloy ingots are produced, and the produced columnar copper alloy ingots are forged, rolled, and cut to form a plate, and then machined. It is applied to complete a product having a predetermined length, width and thickness.

The present inventors have described the composition of the copper alloy constituting the film formed by the sputtering film formation when the sputtering film formation is performed using the copper alloy target composed of copper and nickel produced by the above-mentioned production method. In addition, the causes of variations in the characteristics (for example, electrical resistance value, etc.) of the electrode film and wiring film on which the film was formed were investigated diligently. As a result, it was noticed that the elapsed time used for the sputtering film formation was greatly related to the above variation.
Therefore, the present inventors have determined the elapsed time used for the sputtering film formation, the composition of the copper alloy constituting the film formed by the sputtering film formation, and the characteristics of the electrode film and the wiring film on which the film is formed (for example,). We investigated and analyzed the relationship with (electrical resistance, etc.). As a result, it was found that the cause of the above-mentioned variation is caused by the composition difference in the copper alloy target, and the composition difference is in the columnar copper alloy ingot produced by casting used for manufacturing the copper alloy target. ..

Alloys composed of copper and nickel are known to form a solid solution at all rates.
Therefore, in the case of a columnar copper alloy ingot cast by using a molten copper alloy produced by melting a metal material composed of copper and nickel, it is considered that the composition becomes uniform over the entire region of the copper alloy ingot. Was there.

However, when the present inventors investigated the nickel content of a columnar copper alloy ingot obtained by melting and casting using a metal material composed of copper and nickel, the nickel content was found to be copper alloy casting. It was found that the content of the copper alloy ingot was not uniform over the entire region, and the nickel content in the central region of the copper alloy ingot was higher than that in the peripheral region.

Specifically, the present inventors prepared a molten copper alloy by melting a metal material composed of copper and nickel whose content was adjusted so that the nickel content was 30% by mass. Casting was performed using molten copper alloy to prepare two columnar copper alloy ingots having a diameter of 100 mm and a height of 150 mm as shown in FIG. 5 (a).
Next, each of the produced columnar copper alloy ingots was cut in half along the height direction, and the nickel content at each position of the cut surface shown in FIG. 5 (b) was measured. The nickel content is measured by drilling each position of the cut surface to a depth of 20 mm with a drill, collecting cutting chips obtained by drilling as a sample, and quantitatively analyzing the collected sample using an ICP analyzer. rice field. Then, using this measured value, the difference between the maximum value of the nickel content at all the measured positions of each copper alloy ingot and the average value of the nickel content at all the measured positions of the copper alloy ingot is calculated as the copper alloy. Percentage divided by the average value of the nickel content at all measurement positions of the ingot, the minimum value of the nickel content at all measurement positions of each copper alloy ingot, and the nickel content at all measurement positions of the copper alloy ingot. The difference from the average value of the copper alloy ingot was divided by the average value of the nickel contents at all the measurement positions of the copper alloy ingot, and the percentage was calculated as a numerical value for evaluating the variation in the nickel content in the copper alloy ingot.
The numerical values for evaluation of the variation in the nickel content at each measurement position of each copper alloy ingot and the nickel content in each copper alloy ingot at that time are shown in Tables 1-1 to 1-3 below.
In FIG. 5B, A, B, and C indicate the positions in the height direction on the cut surface of each columnar copper alloy ingot, and 1 to 11 indicate the radial positions on the cut surface. There is. Further, in Tables 1-2 and 1-3, "Area 1-3" is a gathering area of measurement positions specified by positions 1 to 3 in the radial direction and positions A to C in the height direction, "Area 5-". "7" is the gathering area of the measurement positions specified by the radial positions 5 to 7 and the height positions A to C, and "Area 4-8" is the radial positions 4 to 8 and the height position. "Area 9-11" is a gathering area of measurement positions specified by A to C, and "Area 9-11" is a gathering area of measurement positions specified by positions 9 to 11 in the radial direction and positions A to C in the height direction. "Whole" indicates the collective region (all measurement positions) of the measurement positions specified by the positions 1 to 11 in the radial direction and the positions A to C in the height direction, respectively.

Table 1-1 (Nickel content (mass (%)) of the first and second copper alloys)

Table 1-2 (Nickel content (mass (%)) by area of the first and second copper alloys)

Table 1-3 (values for evaluating the variation in nickel content in the first and second copper alloys)

As shown in Tables 1-1 and 1-2, each copper alloy ingot is radial in the area (area 4-8) at the center position in the radial direction (diameter positions 4 to 8). Nickel content is higher than in the peripheral positions (diametric positions 1-3, 9-11) (areas 1-3, 9-11), especially in the radial center position (diameter positions 5-7). In the area (Area 5-7), the nickel content was found to be the highest.
Specifically, the average value of the nickel content in the area (areas 1-3, 9-11) of the radial peripheral positions (diametric positions 1-3, 9-11) is the sample 1 (first copper alloy casting). 30.1% by mass in the mass) and 30.1% by mass in the sample 2 (second copper alloy ingot), whereas it is the center position in the radial direction (positions 4 to 8 in the radial direction). The average value of the nickel content in the area (area 4-8) of) is 31.2% by mass in both sample 1 and sample 2, and further, the center position in the radial direction (positions 5 to 7 in the radial direction). It was found that the average value of the nickel content in the area (area 5-7) of) was 31.5% by mass in both Sample 1 and Sample 2.
The maximum value of the nickel content in the area (area 5-7) at the center position in the radial direction (diameter positions 5 to 7) is 32.3% by mass in sample 1 and 32.6% by mass in sample 2. It was confirmed that the nickel content was the maximum value at all measurement positions (entire area).

Further, as shown in Table 1-3, "the difference between the maximum value of the nickel content at all the measurement positions of each copper alloy ingot and the average value of the nickel content at all the measurement positions of the copper alloy ingot". "Absolute value of percentage divided by the average value of nickel content at all measurement positions of the copper alloy ingot" and "Minimum value of nickel content at all measurement positions of each copper alloy ingot and the copper alloy ingot" The maximum value in "Absolute value of percentage obtained by dividing the difference from the average value of the nickel content at all the measurement positions of the copper alloy ingot by the average value of the nickel content at all the measurement positions of the copper alloy ingot" is 5 in sample 1. It was found that the ratio was 5.5% and that of sample 2 was 6.6%.

If the nickel content in the copper alloy ingot is not uniform over the entire region, the copper alloy target obtained by forging or rolling using the copper alloy ingot to form a plate also contains nickel in the copper alloy target. The amount does not become uniform over the entire region, and the nickel content at each position of the copper alloy target becomes a value corresponding to the copper alloy ingot and the variation becomes large.

For example, a columnar copper alloy ingot cast using a molten copper alloy prepared by melting a metal material is forged, rolled, and cut to form a plate, and then cut to a desired product size. Therefore, when the copper alloy target is produced, the nickel content in the region corresponding to the position near the center of the cross section in the thickness direction of the copper alloy target is higher than the nickel content in the region corresponding to the position near the edge of the cross section. As a result, the nickel content in the target varies.

When an electrode film, a wiring film, or the like was formed by sputtering using such a copper alloy target, the nickel content of the target at the site to be sputtered changed due to the difference in the elapsed time used for sputtering, and was formed by sputtering. The composition of the copper alloy constituting the electrode film, the wiring film, etc., and the characteristics of the electrode film, the wiring film, etc. (for example, the electric resistance value, etc.) may fluctuate and the variation may increase.

Regarding the nickel content in the width direction of the plate-shaped member before the copper alloy target is manufactured, the nickel content in the region corresponding to the center position in the width direction of the plate-shaped member is the peripheral position in the width direction of the plate-shaped member. The nickel content is higher than that in the region corresponding to each position, and the nickel content varies in the region corresponding to each position. As a result, even in individual copper alloy targets manufactured by cutting out a plate-shaped member into a desired product shape and size, the nickel content varies in the target, and the quality of the product cannot be kept constant. There is a risk.

However, as described above, the columnar copper alloy ingot shown in FIG. 5 has a radial peripheral position (diameter) in the area (area 4-8) of the radial center position (diameter position 4 to 8). The nickel content is higher than that of the area (areas 1-3, 9-11) in the direction positions 1 to 3 and 9 to 11), and in particular, the nickel content is higher in the area of the radial positions 5 to 7 (area 5-7). The content is the highest, and the maximum value of nickel content in the area (area 5-7) at the radial center position (diametric position 5-7) is the nickel in all measurement positions (entire area). It is recognized that the content is the maximum value.

Here, the present inventors exclude an area (here, area 5-7) at the radial center position (diameter position 5-7) from the entire area in each of the sample 1 and the sample 2. Area (referred to as "area 5-7 exclusion"), an area excluding the area (area 4-8) at the radial center position (diametric position 4 to 8) from the entire area (here, "area 4-8 exclusion") The average value of the nickel content was calculated using the measured values of the nickel content at all the measurement positions in each area of (referred to as). In addition, the difference between the maximum value of the nickel content at all measurement positions in each area and the average value of the nickel content at all measurement positions in the area is the average value of the nickel content at all measurement positions in the area. The difference between the percentage divided by and the minimum value of the nickel content at all measurement positions in each area and the average value of the nickel content at all measurement positions in the area is the nickel content at all measurement positions in the area. The percentage divided by the average value of the amount was calculated as a numerical value for evaluation of the variation in the nickel content in the area.
The average value of the nickel content at all measurement positions in each area at that time and the numerical value for evaluating the variation in nickel content in each area are used, and the numerical value for evaluating the variation in nickel content at all measurement positions in the entire area. It is also shown in Table 1-4 below.

Table 1-4 (values for evaluation of variation in nickel content in all areas of the first and second copper alloys and when the central area is excluded from all areas)

As shown in Table 1-4, "all measurement positions in the area (area 5-7 excluded) excluding the area (area 5-7) at the radial center position (diametric position 5-7) from the entire area. The absolute value of the percentage obtained by dividing the difference between the maximum value of the nickel content in the area and the average value of the nickel content at all the measurement positions in the area by the average value of the nickel content at all the measurement positions in the area. " "The difference between the minimum value of the nickel content at all measurement positions in the area and the average value of the nickel content at all measurement positions in the area is divided by the average value of the nickel content at all measurement positions in the area. The maximum value in "absolute value of percentage" is 2.0% for sample 1 and 2.3% for sample 2, and the maximum value for the entire area (5.5% for sample 1 and 6 for sample 2). It was found that the variation in nickel content was significantly reduced as compared with 0.6%).

In addition, "the maximum value of the nickel content at all measurement positions in the area (area 4-8 excluded) excluding the area (area 4-8) at the radial center position (diametric position 4 to 8) from the entire area. And "the absolute value of the percentage obtained by dividing the difference between the average value of the nickel content at all the measurement positions in the area and the average value of the nickel content at all the measurement positions in the area" and "all measurements in the area". The absolute value of the percentage obtained by dividing the difference between the minimum value of the nickel content at the position and the average value of the nickel content at all the measurement positions in the area by the average value of the nickel content at all the measurement positions in the area. " The maximum value in, was 0.9% in sample 1 and 0.7% in sample 2, which was compared with the maximum value in the entire area (5.5% in sample 1 and 6.6% in sample 2). Therefore, it was found that the variation in nickel content was further significantly reduced.

Here, the length of the radial center position (diameter positions 5 to 7) shown in FIG. 5B is 5 mm, has a length of 5% of the total diameter of 100 mm, and is the radial center. The length of the position (positions 4 to 8 in the radial direction) is 10 mm, and has a length of 10% of the total diameter of 100 mm.

Therefore, as a measure to reduce the variation in the nickel content in the region corresponding to each thickness position of the copper alloy target composed of copper and nickel, the present inventors have set the nickel content in the columnar copper alloy ingot. High, from the center of the bottom surface of the copper alloy ingot to the outer edge of the bottom surface, it has at least a similarity region having a similarity ratio of 5% to 10% with respect to the bottom surface, and has the same height as the copper alloy ingot. The idea was to remove the central columnar part and then forge and roll to make a copper alloy target.
Then, the present inventors prepare a copper alloy target composed of copper and nickel based on this idea, and when the sputtering film formation is performed using the copper alloy target, the elapsed time used for the sputtering film formation is different. It has been found that the variation in the composition of the copper alloy constituting the film formed by the sputtering film formation can be suppressed as much as possible, and the copper alloy target of the present invention and the method for producing the same have been derived.

Hereinafter, specific embodiments of the copper alloy target of the present invention and the method for producing the same will be described in detail. The present invention is not limited to the following embodiments, and various modifications can be made without changing the gist of the present invention.

<1. Copper alloy target ＞
The copper alloy target of the present embodiment is a copper alloy target composed of an alloy of copper and nickel and containing nickel in a proportion of more than 10% by mass and 50% or less in mass, and the entire region of the copper alloy target. Absolute value of the percentage obtained by dividing the difference between the nickel content at that position and the average value of the nickel content in the entire region of the copper alloy target by the average value of the nickel content in the entire region of the copper alloy target at each position. However, it is 3% or less.

(Nickel content)
If the nickel content in the alloy composed of copper and nickel is set to more than 10% by mass and 50% or less by mass like the copper alloy target of the present embodiment, corrosion resistance, heat resistance, and oxidation resistance are improved. It is possible to improve the electric resistance value of the electrode film, the wiring film, etc. formed by sputtering.
On the other hand, if the nickel content in the copper alloy target is 10% by mass or less, sufficient corrosion resistance, heat resistance, and oxidation resistance cannot be obtained, which is not preferable.
The nickel content in the copper alloy target made of an alloy of copper and nickel has the maximum resistance value at 50% by mass, and the resistance value decreases when it exceeds 50%.

(Variation of nickel content)
Variations in nickel content in each region of the copper alloy target, such as the copper alloy target of the present embodiment (at each position within the entire region of the copper alloy target, the nickel content at that position and the entire region of the copper alloy target). By reducing the difference from the average value of the nickel content in the copper alloy target divided by the average value of the nickel content in the entire region of the copper alloy target), the difference in the elapsed time used for sputtering is used. , The variation in the composition of the copper alloy constituting the electrode film, the wiring film, etc. formed by sputtering can be suppressed as much as possible, and the variation in the characteristics of the electrode film, the wiring film, etc. can be minimized.
When forming an electrode film or wiring film on an electronic component that has become smaller and thinner in recent years, the nickel content and the entire copper alloy target at each position within the entire region of the copper alloy target. It is necessary that the absolute value of the percentage obtained by dividing the difference from the average value of the nickel content of the region by the average value of the nickel content of the entire region of the copper alloy target satisfies 3% or less, and more preferably 1. It should be less than%.

<2. Manufacturing method of copper alloy target ＞
In the method for manufacturing a copper alloy target of the present embodiment, copper and nickel are melted in a vacuum melting furnace to prepare a molten copper alloy, and the prepared molten copper alloy is used for casting to produce a columnar copper alloy ingot. After producing the copper alloy ingot, the copper alloy ingot is cut in half along the height direction, and 5% to the bottom surface from the center of the bottom surface of the copper alloy ingot toward the outer edge of the bottom surface. A central columnar portion having at least a similarity region having a similarity ratio of 10% and having the same height as a copper alloy ingot is cut and removed. After producing the copper alloy ingot, the central columnar portion of the copper alloy ingot may be removed by cutting or the like, and then the copper alloy ingot may be cut in half along the height direction.
As in the method for manufacturing a copper alloy target of the present embodiment, the central columnar portion to be cut and removed is directed from the center of the bottom surface of the copper alloy ingot toward the outer edge of the bottom surface, and is 5% to 10% with respect to the bottom surface. If the copper alloy target has at least a similar region having a similarity ratio of The absolute value of the percentage obtained by dividing the difference from the average value of the nickel content in all regions of the alloy target by the average value of the nickel content in all regions of the copper alloy target can be suppressed to 3% or less, which was used for sputtering. Due to the difference in elapsed time, the variation in the composition of the copper alloy constituting the electrode film, the wiring film, etc. formed by sputtering can be suppressed as much as possible, and the variation in the characteristics of the electrode film, the wiring film, etc. can be minimized.
On the other hand, the central columnar portion to be cut and removed is directed from the center of the bottom surface of the copper alloy ingot toward the outer edge of the bottom surface so as not to have a similarity region having a similarity ratio of 5% with respect to the bottom surface. Then, even if the height of the central columnar portion to be cut and removed is the same as the height of the copper alloy ingot, the nickel content and the copper alloy at each position in the entire region of the produced copper alloy target are obtained. It becomes difficult to suppress the absolute value of the percentage obtained by dividing the difference from the average value of the nickel content in all regions of the target by the average value of the nickel content in all regions of the copper alloy target to 3% or less, and sputtering film formation. Due to the difference in the elapsed time used in the above, it is not possible to sufficiently suppress the variation in the composition of the copper alloy constituting the film formed by the sputtering film formation.
Further, the central columnar portion has a similarity region having a similarity ratio of more than 10% with respect to the bottom surface from the center of the bottom surface of the copper alloy ingot toward the outer edge of the bottom surface, which is the same as the copper alloy ingot. Even if the copper alloy ingot is cut and removed so as to have a height, a similarity region having a similarity ratio of 10% with respect to the bottom surface from the center of the bottom surface of the copper alloy ingot toward the outer edge of the bottom surface. The effect of suppressing the variation in the nickel content in each region of the produced copper alloy target is as compared with the case where the copper alloy ingot is cut and removed so as to have the same height as the copper alloy ingot. Almost the same. Therefore, in order to eliminate waste of the material to be produced, the central columnar portion has a similarity ratio of 10% with respect to the bottom surface from the center of the bottom surface of the copper alloy ingot toward the outer edge of the bottom surface. It is preferable to have a region and have the same height as the copper alloy ingot.
From the center of the bottom surface of the copper alloy ingot to the outer edge of the bottom surface, it has at least a similarity region having a similarity ratio of 5% to 10% with respect to the bottom surface, and has the same height as the copper alloy ingot. Then, the central columnar portion to be cut and removed may have a shape similar to or dissimilar to the copper alloy ingot. The optimum shape can be selected from the viewpoint of cost.

In the copper alloy ingot, nickel is 10 in a state where oxidation is suppressed by introducing an inert gas such as argon gas or nitrogen gas after vacuuming the inside of a sealable chamber such as a high frequency vacuum melting furnace. It is obtained by casting using a molten copper alloy obtained by melting copper and nickel so as to contain the content in a proportion of more than mass% and 50% by mass or less.

When melting metal materials and casting using molten copper alloy, the pressure inside the chamber is reduced to 1 Pa or more and 90,000 Pa or less by introducing an inert gas after vacuuming the inside of the sealable chamber to 0.01 Pa or less. It is desirable to do.

By vacuuming the inside of the chamber to 0.01 Pa or less, oxygen in the chamber can be removed as much as possible, and the amount of oxygen contained (concentration of oxygen contained) and the amount of hydrogen contained (contained) in the obtained copper alloy target can be removed. Hydrogen concentration) can be reduced.

Further, after vacuuming the inside of the chamber, an inert gas such as argon gas or nitrogen gas is introduced to adjust the pressure in the chamber to 1 Pa or more and 90,000 Pa or less, and melting and casting are performed under the pressure. It is possible to prevent gas components such as hydrogen and oxygen from being re-incorporated into the copper alloy without evaporating the copper in the chamber, and the nest inside the ingot, that is, inside the copper alloy target (defect inside the casting). The formation of the cavity) is suppressed, and the occurrence of abnormal discharge can be prevented during sputtering using a copper alloy target.

If the pressure in the chamber after the introduction of the inert gas is less than 1 Pa, the copper evaporates in the chamber while melting the metal material, which makes the viewing window cloudy, resulting in poor workability and oscillation. Evaporated copper may be deposited on all parts of the coil, electrode terminals, etc. In that case, cleaning of the inside of the device is required and maintainability is deteriorated, which is not preferable. On the other hand, when the pressure in the chamber exceeds 90,000 Pa, the gas component contained in the copper alloy is hardly removed during the melting of the metal material and the casting using the molten copper alloy, and the inside of the ingot of the copper alloy and further It is not preferable because a large number of nests are formed inside the copper alloy target and abnormal discharge may occur frequently during sputtering.

Further, in the method for manufacturing a copper alloy target of the present embodiment, next, the copper alloy ingot from which the central columnar portion is removed and cut in half along the height direction is heated to 1,000 ° C. or higher. It is heated to a first temperature below the melting point of copper, and forging is performed on the copper alloy ingot heated to the first temperature.
The above heating at the time of forging is performed in order to facilitate plastic deformation of the copper alloy ingot. However, when the heating temperature for forging a copper alloy ingot becomes a temperature higher than the solid phase line of the copper alloy, a part of the composition is melted and the composition of the copper alloy fluctuates or melts out. It is not preferable because the portion may become a void or the heating device may be damaged by the melted alloy. On the other hand, if the temperature at the time of forging the copper alloy ingot is too low, the copper alloy ingot is too hard and the workability is deteriorated, which may cause cracks, which is not preferable.
However, the melting point of the metal constituting the copper alloy target of the present embodiment is about 1,085 ° C. for copper and 1,455 ° C. for nickel, and the melting point of the copper-nickel alloy which is a total solid solution is the temperature between them. Since the lowest temperature of the solid phase line in the copper alloy ingot used in the method for manufacturing the copper alloy target is about 1,085 ° C of copper, when forging the copper alloy ingot with the central part cut. The first temperature for heating is set to a temperature of 1,000 ° C. or higher in order to lower the melting point of copper and improve workability as much as possible.

Further, in the method for manufacturing a copper alloy target of the present embodiment, next, the forged copper alloy ingot is heated to a second temperature within the range of 900 ° C. ± 100 ° C., and the copper alloy is heated to the second temperature. Hot rolling is repeated for the ingot by changing the processing ratio in multiple stages to form a plate having the first thickness.
When an alloy ingot such as the copper alloy ingot of the present invention is forged or rolled, the alloy structure is generally distorted and hardened. As the curing progresses, it becomes difficult to deform and there is a risk of cracking. Therefore, as described above, when forging a copper alloy ingot or rolling after forging, the material is once heated to release the strain in the alloy structure, and then the plate is adjusted to a predetermined thickness. Form the body. The material is appropriately heated according to the amount of strain generated in the processed material.
The higher the temperature during hot rolling, the better the workability, but the easier it is to oxidize and the more likely it is that an oxide film will be formed on the surface.
Therefore, the second temperature for heating the forged copper alloy ingot during hot rolling is set to a temperature within the range of 900 ° C. ± 100 ° C.

Further, in the method for manufacturing a copper alloy target of the present embodiment, next, the hot-rolled plate body is cold-rolled so as to have a processing ratio of 5% or more to form a plate body having a second thickness. After that, the plate body is heat-treated, and the heat-treated plate body is machined to complete the product of the copper alloy target.
Cold rolling is performed to adjust the surface condition (unevenness) of the plate body for forming the copper alloy target as a product and the thickness accuracy.
The plate body after hot rolling shrinks as the plate body cools, but unevenness may be formed on the surface due to variations in temperature during heating and variations in the amount of strain formed, and the thickness after shrinkage may occur. It is difficult to manufacture a plate with high accuracy because the accuracy of the cylinder may deteriorate.
In the manufacture of copper alloy targets, when making the final product, in order to remove the oxide film on the surface of the plate and to obtain smoothness, machining such as cutting the surface of the plate is performed to shape the product. And adjust the size. In order to reduce the cutting amount at this time as much as possible, it is necessary to accurately manufacture the plate body as the base material in the pre-machining stage.
Therefore, in the manufacturing method of the present embodiment, the plate body after hot rolling is cold-rolled to adjust the surface condition and thickness accuracy of the plate body. Since the plate body after cold rolling does not have cooling after processing unlike hot rolling, the amount of deformation after processing can be reduced as much as possible.
The cold rolling is performed so that the final processing ratio of the plate is 5% or more with respect to the plate before the cold rolling.
If the processing rate is less than 5%, the thickness may become a predetermined thickness before the unevenness of the surface generated during hot rolling is sufficiently eliminated, which is not preferable.

After cold rolling and before machining, the plate is heat treated. The temperature of the heat treatment is about 900 ° C. ± 100 ° C. The heat treatment is performed to adjust the metal structure (eliminate the rolled structure) and to eliminate the internal strain caused by cold working.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.

<< Examples and Comparative Examples >>
<Manufacturing of copper alloy targets>
In each of the examples and the comparative examples, a metal material composed of copper and nickel was prepared so that the nickel content was 30% by mass, and the following treatment was applied to produce a copper alloy target.

After vacuuming the inside of the common treatment chamber in Examples and Comparative Examples to 0.009 Pa or less, each addition was made so that the nickel content was 30% by mass using a high-frequency melting furnace in which argon gas was introduced up to 500 Pa. A metal material composed of copper and nickel, whose amount has been adjusted in advance, is melted to prepare a molten copper alloy, which is held under the above pressure for 10 minutes and then cast into a graphite mold to have a bottom surface having a diameter of 100 mm and a height of 140 mm. A columnar copper alloy ingot was produced.

Example 1
In Example 1, the prepared columnar copper alloy ingot was cut in half along the height direction.
Next, a semi-cylindrical portion (copper alloy) having a semi-circular region having a central diameter of 5 mm at the bottom surface of each semi-cylindrical copper alloy ingot cut in half and having the same height as the copper alloy ingot. Corresponding to the central columnar portion having a similarity region having a similarity ratio of 5% with respect to the bottom surface from the center of the bottom surface of the ingot to the outer edge of the bottom surface and having the same height as the copper alloy ingot). The part to be alloyed was cut and removed.
Next, each semi-cylindrical copper alloy ingot having a semi-circular region having a central diameter of 5 mm and having the same height as the copper alloy ingot was cut is heated to 1,000 ° C. Then, forging was performed on each copper alloy ingot heated to 1,000 ° C.
Next, each forged copper alloy ingot was heated to 900 ° C., and the processing ratio was changed in multiple stages for each copper alloy ingot heated to 900 ° C., and hot rolling was repeated, and the length was 250 mm. , Two plates having a width of 120 mm and a thickness of 16 mm were formed. In mass-produced sputtering equipment, a plate of this size is also used as a copper alloy target for forming an electrode film, wiring film, etc. by sputtering, so one of the plates is used as a copper alloy target. It was used as a sample for measuring the nickel concentration distribution in the body.
Next, the remaining one hot-rolled plate was cold-rolled at a processing rate of 5% or more to form a plate having a thickness of about 6 mm.
After that, the plate body was heat-treated at 900 ° C., and the upper surface of about 0.2 mm and the lower surface of about 0.5 mm were cut by machining to make the plate body thickness of about 5 mm, and further, the plate body was cut. A disk-shaped copper alloy target having a diameter of 75 mm and a thickness of 5 mm was prepared and used as a sample for evaluation of sputtering.

Example 2
In Example 2, after cutting the produced columnar copper alloy ingot in half along the height direction, a half having a central diameter of 10 mm on the bottom surface of each semi-cylindrical copper alloy ingot cut in half. Semi-cylindrical portion having a circular region and having the same height as the copper alloy ingot (from the center of the bottom surface of the copper alloy ingot toward the outer edge of the bottom surface, the similarity ratio is 10% with respect to the bottom surface. The central columnar portion, which has a region and is the same height as the copper alloy ingot), was cut and removed.
Next, forging is performed in the same manner as in Example 1, and hot rolling is repeated after forging to form two plates having a length of 240 mm, a width of 120 mm, and a thickness of 16 mm, and one of them is used as a copper alloy target. It was used as a sample for measuring the nickel concentration distribution in the plate.
Then, the remaining one plate is cold-rolled in the same manner as in Example 1 to form a plate having a thickness of about 6 mm, and then heat-treated in the same manner as in Example 1 and machined to have a diameter of 75 mm. A disk-shaped copper alloy target having a thickness of 5 mm was prepared and used as a sample for sputtering evaluation.

Comparative Example 1
In Comparative Example 1, the produced columnar copper alloy ingot was heated to 1,000 ° C. without performing the cutting treatment and the removal treatment of the central columnar portion as in Examples 1 and 2. Forging was performed on a copper alloy ingot heated to 000 ° C. In addition, in order to prepare two kinds of samples for evaluation, two columnar copper alloy ingots were used in Comparative Example 1.
Next, forging is performed in the same manner as in Example 1, and hot rolling is repeated after forging to form two plates having a length of 523 mm, a width of 120 mm, and a thickness of 16 mm, and one of them is used as a copper alloy target. It was used as a sample for measuring the nickel concentration distribution in the plate.
Then, the remaining one plate is cold-rolled in the same manner as in Example 1 to form a plate having a thickness of about 6 mm, and then heat-treated in the same manner as in Example 1 and machined to have a diameter of 75 mm. A disk-shaped copper alloy target having a thickness of 5 mm was prepared and used as a sample for sputtering evaluation.

Comparative Example 2
In Comparative Example 2, after cutting the produced columnar copper alloy ingot in half along the height direction, 1,000 without performing the removal treatment of the central columnar portion as in Examples 1 and 2. Forging was performed on each copper alloy ingot heated to ° C. and heated to 1,000 ° C.
Next, as in Example 1, hot rolling is repeated after forging to form two plates having a length of 260 mm, a width of 120 mm, and a thickness of 16 mm, and one plate is used as a copper alloy target. It was used as a sample for measuring the nickel concentration distribution in.
Then, the remaining one plate is cold-rolled in the same manner as in Example 1 to form a plate having a thickness of about 6 mm, and then heat-treated in the same manner as in Example 1 and machined to have a diameter of 75 mm. A disk-shaped copper alloy target having a thickness of 5 mm was prepared and used as a sample for sputtering evaluation.

<Evaluation>
The following evaluations were carried out using the plate bodies formed by hot rolling in Examples 1 and 2 and Comparative Examples 1 and 2 and the finally prepared copper alloy target as samples.

Evaluation 1: Variation evaluation of nickel content at each measurement position of the plate used as the copper alloy target FIG. 2 shows the measurement of the nickel content in the plate used as the copper alloy target according to each embodiment of the present invention. In the explanatory view showing the position, (a) is a plan view showing each measurement position specified in the length direction and the width direction of the plate body of Example 1, and (b) is the length direction of the plate body of Example 2. And a plan view showing each measurement position specified in the width direction, (c) is a cross-sectional view showing each measurement position specified in the width direction and the thickness direction of each of the plates (a) and (b). .. FIG. 3 is an explanatory view showing the measurement position of the nickel content in the plate body used as the copper alloy target according to each comparative example of the present invention, and (a) is the length direction and width of the plate body of the comparative example 1. A plan view showing each measurement position specified in the direction, (b) is a plan view showing each measurement position specified in the length direction and the width direction of the plate body of Comparative Example 2, (c) is (a), (b) It is sectional drawing which shows each measurement position specified in the width direction and the thickness direction of each plate body.

In this evaluation, with respect to the plate body used as the copper alloy target formed by hot rolling in each of Examples 1 and 2 and Comparative Examples 1 and 2, four points (4 points) in the length direction of each plate body ( A, B, C, D), 3 points in the width direction (1, 2, 3), 3 points in the thickness direction (upper, middle, lower), a total of 36 measurement positions were set.
Then, with respect to each plate, the measurement position is measured from the end on the measurement position A side in the length direction (the left side in FIGS. 2 (a), 2 (b), 3 (a), and 3 (b)). The end face of the measurement position A was made to appear by cutting up to the boundary portion of A.
Next, with respect to the end face of the measurement position A, the nine measurement positions (see FIGS. 2 (c) and 3 (c)) specified in the width direction and the thickness direction are shown in FIGS. 2 (a) and 2 (a). As shown in FIGS. 2 (b), 3 (a), and 3 (b), a drill with a diameter of 3 mm was used to excavate a depth of 20 mm.
Then, the cutting chips obtained by excavation were collected as a sample, and the collected sample was quantitatively analyzed using a predetermined ICP analyzer to measure the nickel content.
Regarding other measurement positions, the plate body is cut up to the boundary of each measurement position (measurement position B, C or D) in the length direction so that the end face of the measurement position appears. With respect to the end face of the measurement position, each of the nine measurement positions specified in the width direction and the thickness direction was excavated to a depth of 20 mm with a φ3 mm drill, and the cutting chips obtained by the excavation were collected as a sample. Quantitative analysis was performed on the collected sample using a predetermined ICP analyzer, and the nickel content was measured. Then, using this measured value, the difference between the maximum value of the nickel content at all the measured positions of each plate and the average value of the nickel content at all the measured positions of the plate is set to the total measured position of the plate. The difference between the percentage divided by the average value of the nickel content of each plate, the minimum value of the nickel content at all measurement positions of each plate, and the average value of the nickel content at all measurement positions of the plate is the plate. The percentage divided by the average value of the nickel content at all the measurement positions of the above was calculated as a numerical value for evaluation of the variation in the nickel content in the plate.
Variations in nickel content and nickel content in the plate at each measurement position of the plate used as the copper alloy target formed by hot rolling in Examples 1 and 2 and Comparative Examples 1 and 2 respectively. The numerical values for evaluation are shown in Table 2-1 to 2-4 below.

Table 2-1 (Examples 1 and 2: Nickel content (% by mass) of the plate)

Table 2-2 (Examples 1 and 2: Numerical values for evaluation of variation in nickel content in the plate)

Table 2-3 (Comparative Examples 1 and 2: Nickel content (% by mass) of the plate)

Table 2-4 (Comparative Examples 1 and 2: Numerical values for evaluation of variation in nickel content in the plate)

Evaluation 2: Evaluation of variation in nickel content in coatings such as electrode films and wiring films formed by sputtering due to differences in the elapsed sputtering time FIG. 4 shows the evaluation of the variation in nickel content in the copper alloy targets of the Examples and Comparative Examples of the present invention. It is explanatory drawing which shows the measuring method of the resistance value with respect to the coating film formed on the glass substrate by sputtering.
In this evaluation, the prepared copper alloy targets in Examples 1 and 2 and Comparative Examples 1 and 2 were used, and a glass substrate having a length and width of 50 mm and a thickness of 0.1 mm was subjected to a predetermined sputtering device. , Sputtering was performed, and the nickel content and the electric resistance value in the coating film such as the electrode film and the wiring film formed by the sputtering at the time of passing the predetermined sputtering were measured.

Specifically, first, a glass substrate is installed in the chamber of the sputtering apparatus, and after the vacuum degree in the chamber ^{reaches 1 × 10 -3} Pa, argon gas is supplied so as to be 15 SCCM until a predetermined time. The sputtering device was operated with the shutter closed so that the coating did not adhere to the glass substrate, and sputtering was performed. After a predetermined time had elapsed, the operation of the sputtering device was temporarily stopped and the copper alloy target was dug. The amount (depth) was measured.
After that, the sputtering device is operated, the shutter is opened to perform sputtering, a film having a film thickness of 0.5 μm is formed on the glass substrate, the shutter is closed, the operation of the sputtering device is temporarily stopped, and the sputtering film is formed. The old glass substrate was removed and a new glass substrate was installed.
Further, the glass substrate on which the film was formed at this time was used as an evaluation sample at a predetermined time point.
After that, with the shutter closed, the sputtering device is operated again to perform sputtering, and when the cumulative sputtering time elapses, the operation of the sputtering device is temporarily stopped, and the copper alloy is used in the same manner as in the first sputtering test. The amount (depth) at which the target was dug was measured, and a film was formed on the glass substrate.
By repeating these treatments, an evaluation sample in which a sputtering film having a thickness of 0.5 μm was formed at each elapsed time of sputtering was obtained.
In this evaluation, the time points for obtaining the evaluation sample are 0.5 (h), 1, 5 (h), 10 (h), 15 (h), 20 (h), 25 (h), and 30 (h). ).

Next, the electric resistance value of the coating film in each of the obtained evaluation samples was measured by a four-terminal four-probe method as shown in FIG. 4 using a predetermined resistance measuring device. Then, using this measured value, the difference between the maximum value of the electric resistance value at the time of all the sputtering of each coating and the average value of the electric resistance at the time of all the sputtering of the coating is set at the time of all the sputtering of the coating. The difference between the percentage divided by the average value of the electrical resistance and the minimum value of the electrical resistance at the time of all sputtering of each coating and the average value of the electrical resistance at the time of total sputtering is the difference between the total sputtering of the coating. The percentage divided by the average value of the electric resistance value at the time point was calculated as a numerical value for evaluation of the variation in the electric resistance value in the coating film.
Then, the coating film formed on the glass substrate was melted for each evaluation sample, and quantitative analysis was performed using a predetermined ICP analyzer to measure the nickel content. Then, using this measured value, the difference between the maximum value of the nickel content at the time of the entire sputtering of each coating and the average value of the nickel content at the time of the entire sputtering is calculated at the time of the entire sputtering of the coating. The difference between the percentage divided by the average nickel content and the minimum nickel content at the time of total sputtering of each coating and the average nickel content at the time of total sputtering is the difference between the total sputtering progress of the coating. The percentage divided by the average value of the nickel content at the time point was calculated as a numerical value for evaluation of the variation in the nickel content in the coating film.
Using the prepared copper alloy targets in Examples 1 and 2 and Comparative Examples 1 and 2, the amount (depth) at which the copper alloy target was dug at a predetermined sputtering stage, and the amount of the copper alloy target dug on the glass substrate by sputtering. The following Tables 3-1 to 3-3 show the numerical values for evaluating the variation in the nickel content of the formed coating and the nickel content in the coating, and the numerical values for evaluating the variation in the electrical resistance value of the coating and the electrical resistance value in the coating. And are shown in Tables 4-1 to 4-3.

Table 3-1 (Examples 1 and 2, Comparative Examples 1 and 2: Nickel content (% by mass) of the coating film)

Table 3-2 (Examples 1 and 2: Numerical values for evaluation of variation in nickel content in the coating)

Table 3-3 (Comparative Examples 1 and 2: Numerical values for evaluation of variation in nickel content in the coating)

Table 4-1 (Examples 1 and 2, Comparative Examples 1 and 2: Electrical resistance of the coating (μΩ · cm))

Table 4-2 (Examples 1 and 2: Numerical values for evaluation of variation in electrical resistance in the coating)

Table 4-3 (Comparative Examples 1 and 2: Numerical values for evaluating variations in electrical resistance in the coating)

<Evaluation result>
Evaluation result 1: Variation of nickel content at each measurement position of the plate used as the copper alloy target Evaluation result The plates used as the copper alloy target of Examples 1 and 2 are shown in Tables 2-1 and 2-2. As shown in, "The absolute value of the percentage obtained by dividing the difference between the maximum value of the nickel content at all measurement positions and the average value of the nickel content at all measurement positions by the average value of the nickel content at all measurement positions". , "Absolute value of percentage obtained by dividing the difference between the minimum value of nickel content at all measurement positions and the average value of nickel content at all measurement positions by the average value of nickel content at all measurement positions", and the maximum value in However, it was 2.0% in Example 1 and 1.0% in Example 2, both of which were within 3%, and it was confirmed that the variation in the nickel content at each measurement position of the plate was suppressed to a small extent. It became.
On the other hand, as shown in Tables 2-3 and 2-4, the plate used as the copper alloy target of Comparative Examples 1 and 2 has "the maximum value of nickel content at all measurement positions and all measurement positions. The absolute value of the percentage obtained by dividing the difference from the average nickel content by the average nickel content at all measurement positions, and the minimum nickel content at all measurement positions and the nickel content at all measurement positions. The maximum value in "the absolute value of the percentage obtained by dividing the difference from the average value by the average value of the nickel contents at all measurement positions" is 5.3% in Comparative Example 1 and 4.6% in Example 2. In each case, it greatly exceeded 3%, and it was confirmed that the nickel content at each measurement position of the plate had a large variation.

Evaluation result 2: Variations in nickel content in coatings such as electrode films and wiring films formed by sputtering due to differences in elapsed sputtering time Evaluation results As shown in Tables 3-1 and 3-2, Examples 1 and 1. A copper alloy target made from a plate that is the base material of the copper alloy target of 2 (a plate with the same composition and size as the plate used as the copper alloy target used in evaluation 1) is formed by sputtering. The film is "percentage of the difference between the maximum nickel content at the time of all sputtering and the average nickel content at the time of all sputtering divided by the average value of nickel content at the time of all sputtering. Percentage of "absolute value" and "difference between the minimum value of nickel content at the time of all sputtering and the average value of nickel content at the time of all sputtering divided by the average value of nickel content at the time of all sputtering" The maximum value in "absolute value" is 1.3% in Example 1 and 0.6% in Example 2, resulting in an electrode film, a wiring film, etc. formed by sputtering due to the difference in elapsed sputtering time. As a result, it was confirmed that the variation in the nickel content in the coating film was suppressed to a small level.
On the other hand, the coating film formed by sputtering the copper alloy target produced from the plate body used as the base material of the copper alloy targets of Comparative Examples 1 and 2 is as shown in Tables 3-1 and 3-3. , "Absolute percentage of the difference between the maximum nickel content at all sputterings and the average nickel content at all sputterings divided by the average nickel content at all sputterings""The absolute value of the percentage obtained by dividing the difference between the minimum nickel content at the time of total sputtering and the average nickel content at the time of total sputtering by the average value of nickel content at the time of total sputtering. The maximum value in Comparative Example 1 is 4.2% and Comparative Example 2 is 3.8%, and nickel in the coating film such as the electrode film and wiring film formed by sputtering due to the difference in the elapsed sputtering time. The result was that the variation in the content was large.

Further, as shown in Tables 4-1 and 4-2, the coating film formed by using the copper alloy target produced from the plate body as the base material of the copper alloy targets of Examples 1 and 2 for sputtering is ". The absolute value of the percentage obtained by dividing the difference between the maximum value of the electric resistance value at the time of all the sputtering and the average value of the electric resistance at the time of all the sputtering by the average value of the electric resistance at the time of all the sputtering. ""The absolute value of the percentage obtained by dividing the difference between the minimum value of the electric resistance value at the time of all the sputtering and the average value of the electric resistance at the time of all the sputtering by the average value of the electric resistance at the time of all the sputtering". The maximum value in (1) is 1.3% in Example 1 and 0.3% in Example 2, and the electric resistance value in the film such as the electrode film or the wiring film formed by sputtering due to the difference in the elapsed sputtering time As a result, it was confirmed that the variation of the electric power was suppressed to a small extent.
On the other hand, the coating film formed by using the copper alloy target produced from the plate body used as the base material of the copper alloy targets of Comparative Examples 1 and 2 for sputtering is as shown in Tables 4-1 and 4-3. , "Absolute value of the percentage obtained by dividing the difference between the maximum value of the electric resistance value at the time of all the sputtering and the average value of the electric resistance at the time of all the sputtering by the average value of the electric resistance at the time of all the sputtering". "The absolute value of the percentage obtained by dividing the difference between the minimum value of the electric resistance value at the time of all the sputtering and the average value of the electric resistance at the time of all the sputtering by the average value of the electric resistance at the time of all the sputtering. The maximum value in Comparative Example 1 is 5.0% and that in Comparative Example 2 is 4.3%, and the electricity in the coating film such as the electrode film or wiring film formed by sputtering due to the difference in the elapsed sputtering time. The result was that the variation in resistance value was large.

From these evaluation results, it is used as the copper alloy target of Examples 1 and 2 (the difference between the maximum value of the nickel content at all the measurement positions and the average value of the nickel content at all the measurement positions of the plate body is all. The difference between the "absolute value of the percentage divided by the average value of the nickel content at the measurement positions" and the "minimum value of the nickel content at all measurement positions and the average value of the nickel content at all measurement positions" is the nickel at all measurement positions. The maximum value in "absolute value of the percentage divided by the average value of the content" is 3% or less.) A copper alloy target made using a plate having the same composition and size as the plate as a base material is used for sputtering. The film formed as an electrode film, wiring film, etc. is the difference between the maximum value of the nickel content at the time of total sputtering and the average value of the nickel content at the time of total sputtering of the copper alloy target. The total difference between the "absolute value of the percentage divided by the average value of the nickel content at the elapsed time" and the "minimum value of the nickel content at the elapsed time of all sputtering and the average value of the nickel content at the elapsed time of all sputtering". The maximum value in "absolute value of the percentage divided by the average value of the nickel content at the time of passing the sputtering" is 1.3%, and "the maximum value of the electric resistance value at the time of passing all the sputtering and the electricity at the time of passing all the sputtering". "Absolute value of the percentage obtained by dividing the difference from the average resistance value by the average value of the electric resistance values at the time of all the sputterings" and "the minimum value of the electric resistance values at the time of all the sputterings and the time of all the sputterings" The maximum value in "absolute value of the percentage obtained by dividing the difference from the average value of the electric resistance value by the average value of the electric resistance values at the time of all sputtering" is 1.3%, regardless of the elapsed sputtering time. It is observed that a film such as an electrode film or a wiring film having a small variation in nickel content is formed.
In particular, a central columnar portion having a similarity region having a similarity ratio of 10% with respect to the bottom surface from the center of the bottom surface of the copper alloy ingot to the outer edge of the bottom surface and having the same height as the copper alloy ingot. Is used as the copper alloy target of Example 2 produced by cutting and removing (the difference between the maximum value of the nickel content at all the measurement positions and the average value of the nickel content at all the measurement positions of the plate body is all. The difference between the "absolute value of the percentage divided by the average value of the nickel content at the measurement positions" and the "minimum value of the nickel content at all measurement positions and the average value of the nickel content at all measurement positions" is the nickel at all measurement positions. Absolute value of the percentage divided by the average value of the content "and the maximum value is 1.0%.) A copper alloy target made using a plate having the same composition and size as the plate as a base material is used for sputtering. For the coating film to be the electrode film, wiring film, etc. formed using the copper alloy target, the difference between the maximum value of the nickel content at the time of total sputtering and the average value of the nickel content at the time of total sputtering is the total. The difference between the "absolute value of the percentage divided by the average value of the nickel content at the time of passing the sputtering" and the "minimum value of the nickel content at the time of passing all the sputtering and the average value of the nickel content at the time of passing all the sputtering". The maximum value in "absolute value of the percentage divided by the average value of the nickel content at the time of all sputtering" and "the maximum value of the electric resistance value at the time of all sputtering" and "the maximum value of the electric resistance value at the time of all sputtering""Absolute value of the percentage obtained by dividing the difference from the average value of the electric resistance value by the average value of the electric resistance value at the time of all the sputtering" and "the minimum value of the electric resistance value at the time of all the sputtering and at the time of all the sputtering" The maximum value in "Absolute value of the percentage obtained by dividing the difference from the average value of the electric resistance value of the above by the average value of the electric resistance value at the time of all sputtering" is 0.3%, regardless of the elapsed time of sputtering. However, it is observed that a film such as an electrode film or a wiring film having extremely small variation is formed.

On the other hand, it is used as the copper alloy target of Comparative Examples 1 and 2 (the difference between the maximum value of the nickel content at all measurement positions and the average value of the nickel content at all measurement positions of the plate is the difference between all measurement positions. Absolute value of the percentage divided by the average value of the nickel content of all measurement positions and "the difference between the minimum value of the nickel content at all measurement positions and the average value of the nickel content at all measurement positions" is the nickel content at all measurement positions. The maximum value in "absolute value of the percentage divided by the average value of" is 4.6% (5.3% in Comparative Example 1). A plate having the same composition and size as the plate is used as the base material. The film that becomes the electrode film, wiring film, etc. formed by using the prepared copper alloy target for sputtering is the "maximum nickel content at the time of total sputtering and the nickel content at the time of total sputtering" of the copper alloy target. Absolute value of the percentage obtained by dividing the difference from the average value of The maximum value in "absolute value of the percentage obtained by dividing the difference from the average value of the amount by the average value of the nickel content at the time of all sputtering" is 3.8% (± 4.2% in Comparative Example 1). "The absolute value of the percentage obtained by dividing the difference between the maximum value of the electric resistance value at the time of all sputtering and the average value of the electric resistance value at the time of all sputtering by the average value of the electric resistance value at the time of all sputtering". , "Absolute value of the percentage obtained by dividing the difference between the minimum value of the electric resistance value at the time of all sputtering and the average value of the electric resistance value at the time of all sputtering by the average value of the electric resistance value at the time of all sputtering". The maximum value of the above is 4.3% (5.0% in Comparative Example 1), and the variation in the characteristics of the film to be formed such as the electrode film and the wiring film becomes large depending on the elapsed sputtering time. Is recognized.

In the copper alloy target of the present invention and the manufacturing method thereof, an electrode film, a wiring film, etc. of electronic parts are formed by sputtering using a copper alloy target made of a metal material that forms a total solid solution such as an alloy composed of copper and nickel. It is useful in fields where it is required to do.

Claims (6)

A copper alloy target composed of an alloy of copper and nickel and containing nickel in an amount of more than 10% by mass and 50% by mass or less.
The difference between the nickel content at each position in the entire region of the copper alloy target and the average value of the nickel content in the entire region of the copper alloy target is the nickel content in the entire region of the copper alloy target. A copper alloy target characterized in that the absolute value of the percentage divided by the average value of is 3% or less. The difference between the nickel content at each position in the entire region of the copper alloy target and the average value of the nickel content in the entire region of the copper alloy target is the nickel content in the entire region of the copper alloy target. The copper alloy target according to claim 1, wherein the absolute value of the percentage divided by the average value of is 1% or less. The process of melting copper and nickel in a vacuum melting furnace to prepare a molten copper alloy,
The process of producing a columnar copper alloy ingot by casting using the prepared molten copper alloy, and
After producing the copper alloy ingot, the copper has at least a similarity region having a similarity ratio of 5% to 10% with respect to the bottom surface from the center of the bottom surface of the copper alloy ingot toward the outer edge of the bottom surface. A step of removing the central columnar portion from the copper alloy ingot, which has the same height as the alloy ingot,
After producing the copper alloy ingot, the step of cutting the copper alloy ingot in half along the height direction and
A method for manufacturing a copper alloy target, which comprises. The central columnar portion was removed, and the copper alloy ingot cut in half along the height direction was heated to a first temperature of 1,000 ° C. or higher and lower than the melting point of copper. The method for manufacturing a copper alloy target according to claim 3, further comprising a step of forging the copper alloy ingot heated to the temperature of 1. The forged copper alloy ingot is heated to a second temperature within the range of 900 ° C. ± 100 ° C., and the processing rate is changed in multiple stages with respect to the copper alloy ingot heated to the second temperature to heat. The method for manufacturing a copper alloy target according to claim 4, further comprising a step of repeatedly performing inter-rolling to form a plate having a first thickness. The hot-rolled plate was cold-rolled so that the processing ratio was 5% or more to form a plate having a second thickness, and then the plate was heat-treated and heat-treated. The method for manufacturing a copper alloy target according to claim 5, wherein the plate body is machined to complete a product of the copper alloy target.

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